Bromine-magnesium-exchange as a general tool for the preparation of polyfunctional aryl and heteroaryl magnesium-reagents

Tetrahedron Letters

Volumn 40, Issue 42, 1999, Pages 7449-7453

  Abarbri, Mohamed ^a   Dehmel, Florian ^a   Knochel, Paul ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

BROMINE; MAGNESIUM; MAGNESIUM DERIVATIVE; ORGANOMETALLIC COMPOUND; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; POLYFUNCTIONAL GROUP; REAGENT;

ARTICLE; CHEMICAL REACTION; SYNTHESIS;

EID: 0033570284     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01404-5     Document Type: Article

References (22)

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5. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
6. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
7. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
8. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
9. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
10. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
11. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
12. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
13. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
14. For some examples of halogen-magnesium-exchange reactions: (a) Villiéras, J. Bull. Soc. Chim. Fr. 1967, 1520; (b) Paradies, H. H.; Görbing, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 279; (c) Smith, C. F.; Moore, G. J.; Tamborski, C. J. Organomet. Chem. 1971, 33, C21; (d) Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 107; (e) Seyferth, D.; Lambert, R. J. Organomet. Chem. 1973, 54, 123; (f) Redwane, N.; Moreau, P.; Commeyras, A. J. Fluorine Chem. 1982, 20, 699; (g) Furukawa, N.; Shibutani, T.; Fujihara, H. Tetrahedron Lett. 1987, 28, 5845; (h) Nishiyama, H.; Isaka, K.; Itoh, K.; Ohno, H.; Nagase, K.; Matsumoto, K.; Yoshiwara, H. J. Org. Chem. 1992, 57, 407; (i) Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349; (j) Trécourt, F.; Breton, G.; Mongin, F.; Marsais, F.; Quéguiner, G. Tetrahedron Lett. 1999, 40, 4339.
15. Snieckus, V. Chem. Rev. 1990, 90, 879.
16. For a bromine-lithium exchange reaction on tribromoimidazoles see: Lipshutz, B. H.; Hagen, W. Tetrahedron Lett. 1992, 33, 5865.
17. (a) Cai, D.; Hughes, D. L.; Verhoeven, T. R. Tetrahedron Lett. 1996, 35, 2537; (b) Quéguiner, G.; Marsais, F.; Snieckus, V.; Epsztajn, J. Advances of Heterocyclic Chemistry 52, pp. 189-304, Academic Press: San Diego, 1991.
18. (a) Cai, D.; Hughes, D. L.; Verhoeven, T. R. Tetrahedron Lett. 1996, 35, 2537; (b) Quéguiner, G.; Marsais, F.; Snieckus, V.; Epsztajn, J. Advances of Heterocyclic Chemistry 52, pp. 189-304, Academic Press: San Diego, 1991.
19. Rho, T.; Abuh, Y. F. Synth. Commun. 1994, 24, 253.
20. (a) Hartley, D. J.; Iddon, B. Tetrahedron Lett. 1997, 38, 4647; (b) O'Connell, J. F.; Parquette, J.; Yelle, W. E.; Wang, W.; Rapoport, H. Synthesis 1988, 767.
21. (a) Hartley, D. J.; Iddon, B. Tetrahedron Lett. 1997, 38, 4647; (b) O'Connell, J. F.; Parquette, J.; Yelle, W. E.; Wang, W.; Rapoport, H. Synthesis 1988, 767.
22. Typical procedure. Preparation of 2-bromo-5-(1-hydrobenzyl)thiophene (11j; entry 10 of Table 1). A dry three-necked flask equipped with a magnetic stirring bar and a septum was charged with 2,5-dibromothiophene (10h; 800 mg, 3.3 mmol) in THF (2 mL) and was cooled to -5°C. i-PrMgBr (5.7 mL, 4 mmol, 0.7 M in THF) was added dropwise and the reaction mixture was stirred at -5°C for 0.5 h. Benzaldehyde (445 mg, 4.2 mmol) was added and the reaction mixture was warmed to 0°C. After the typical workup, the crude product was purified by flash chromatography (pentane:ether 7:3) yielding the desired product as a white solid (657 mg, 74% yield; mp=62°C).